The present review was aimed at describing the state-of-the-art, for the period January 2011–December 2012, of two pillar classes of phosphorus-containing compounds, the phosphonium salts and ylides. For the Reader’s convenience, topics are organized to offer an introductory survey on the methods of preparation and characterisation of both types of compounds, followed by an analysis of the most remarkable but also curiosity driven researches for their applications. A special section is devoted to phosphonium-based ionic liquids (PIls) due to the exceptional importance of this topic.